Fe L-edge X-ray absorption spectroscopy of low-spin heme relative to non-heme Fe complexes: delocalization of Fe d-electrons into the porphyrin ligand

Hemes (iron porphyrins) are involved in a range of functions in biology, including electron transfer, small-molecule binding and transport, and O2 activation. The delocalization of the Fe d-electrons into the porphyrin ring and its effect on the redox chemistry and reactivity of these systems has been difficult to study by optical spectroscopies due to the dominant porphyrin pi-->pi(*) transitions, which obscure the metal center. Recently, we have developed a methodology that allows for the interpretation of the multiplet structure of Fe L-edges in terms of differential orbital covalency (i.e., differences in mixing of the d-orbitals with ligand orbitals) using a valence bond configuration interaction (VBCI) model. Applied to low-spin heme systems, this methodology allows experimental determination of the delocalization of the Fe d-electrons into the porphyrin (P) ring in terms of both P-->Fe sigma and pi-donation and Fe-->P pi back-bonding. We find that pi-donation to Fe(III) is much larger than pi back-bonding from Fe(II), indicating that a hole superexchange pathway dominates electron transfer. The implications of the results are also discussed in terms of the differences between heme and non-heme oxygen activation chemistry.     

Bis(μ-oxo) dicopper(III) species of the simplest peralkylated diamine: enhanced reactivity toward exogenous substrates

N,N,N',N'-tetramethylethylenediamine (TMED), the simplest and most extensively used peralkylated diamine ligand, is conspicuously absent from those known to form a bis(μ-oxo)dicopper(III) (O) species, [(TMED)(2)Cu(III)(2)(μ(2)-O)(2)](2+), upon oxygenation of its Cu(I) complex. Presented here is the characterization of this O species and its reactivity toward exogenous substrates. Its formation is complicated both by the instability of the [(TMED)Cu(I)](1+) precursor and by competitive formation of a presumed mixed-valent trinuclear [(TMED)(3)Cu(III)Cu(II)(2)(μ(3)-O)(2)](3+) (T) species. Under most reaction conditions, the T species dominates, yet, the O species can be formed preferentially (>80%) upon oxygenation of acetone solutions, if the copper concentration is low (<2 mM) and [(TMED)Cu(I)](1+) is prepared immediately before use. The experimental data of this simplest O species provide a benchmark by which to evaluate density functional theory (DFT) computational methods for geometry optimization and spectroscopic predictions. The enhanced thermal stability of [(TMED)(2)Cu(III)(2)(μ(2)-O)(2)](2+) and its limited steric demands compared to other O species allows more efficient oxidation of exogenous substrates, including benzyl alcohol to benzaldehyde (80% yield), highlighting the importance of ligand structure to not only enhance the oxidant stability but also maintain accessibility to the nascent metal/O(2) oxidant.     

Preparation,characterisation and electrochromic property of mesostructured tungsten oxide films via a surfactant templated sol–gel process from tungstic acid

A novel kind of mesoporous tungsten oxide films (TOFs) has been prepared via a non-ionic surfactant templated sol–gel route from cheap and easy handling tungstic acid. Characterisations by means of various techniques, including XRD, TEM, SEM, ATR and DTA, confirm that the obtained mesostructures are composed of fine mesopores (2–3 nm) and thin pore walls. Compared with previously reported surfactant templated mesoporous TOFs, our initial evaluation on the electrochromic properties showed that the derived TOFs show greatly enhanced colouration efficiency of 44 cm² C⁻¹ and faster colouration/bleaching speed of 10/2 s, respectively. Owing to the ordering of mesostructures delivered by our method, the mesostructural changes associated with the electrochemical reaction during the electrochromic cycling of such materials can be directly monitored by low-angle XRD measurements.     

One-pot cross-metathesis/tandem carbonyl ylide formation-intramolecular cycloaddition of an unsaturated 2-diazo-3,6-diketoester

Dicarbonyl-stabilised diazo functionality is tolerated during alkene cross-metathesis using Grubbs' catalyst, but undergoes subsequent tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition on addition of catalytic Rh2(OAc)4 in a one-pot operation.     

Dioxygen reactivity of a copper(I) complex with a N3S thioether chelate; peroxo-dicopper(II) formation including sulfur-ligation

Employing a tetradentate N3S(thioether) ligand, LN3S, dioxygen reactivity of a copper(I) complex, [(LN3S)CuI]+ (1) was examined. In CH2Cl2, acetone (at -80 degrees C), or 2-methyltetrahydrofuran (at -128 degrees C), 1 reacts with O2 producing the end-on bound peroxodicopper(II) complex [{(LN3S)CuII}2(mu-1,2-O2(2-))]2+ (2), the first reported copper-dioxygen adduct with sulfur (thioether) ligation. Its absorption spectrum contains an additional low-energy feature (but not a Cu-S CT band) compared to the previously well-characterized N4 ligand complex, [{(TMPA)CuII}2(mu-1,2-O2(2-))]2+ (3) (TMPA = tris(2-pyridylmethyl)amine). Resonance Raman spectroscopy confirms the peroxo formulation {nu(O-O) = 817 cm-1 (16-18O2 Delta = 46 cm-1) and nu(Cu-O) = 545 cm-1 (16-18O2 Delta = 26 cm-1), in close analogy to that known for 3 {nu(O-O) = 827 cm-1 and nu(Cu-O) = 561 cm-1}. Direct evidence for thioether ligation comes from EXAFS spectroscopy {Cu K-edge; Cu-S = 2.4 A}.     

Experimental evaluation of radiosity for room sound-field prediction

An acoustical radiosity model was evaluated for how it performs in predicting real room sound fields. This was done by comparing radiosity predictions with experimental results for three existing rooms--a squash court, a classroom, and an office. Radiosity predictions were also compared with those by ray tracing--a "reference" prediction model--for both specular and diffuse surface reflection. Comparisons were made for detailed and discretized echograms, sound-decay curves, sound-propagation curves, and the variations with frequency of four room-acoustical parameters--EDT, RT, D50, and C80. In general, radiosity and diffuse ray tracing gave very similar predictions. Predictions by specular ray tracing were often very different. Radiosity agreed well with experiment in some cases, less well in others. Definitive conclusions regarding the accuracy with which the rooms were modeled, or the accuracy of the radiosity approach, were difficult to draw. The results suggest that radiosity predicts room sound fields with some accuracy, at least as well as diffuse ray tracing and, in general, better than specular ray tracing. The predictions of detailed echograms are less accurate, those of derived room-acoustical parameters more accurate. The results underline the need to develop experimental methods for accurately characterizing the absorptive and reflective characteristics of room surfaces, possible including phase.     

Auralization study of optimum reverberation times for speech intelligibility for normal and hearing-impaired listeners in classrooms with diffuse sound fields

Speech-intelligibility tests auralized in a virtual classroom were used to investigate the optimal reverberation times for verbal communication for normal-hearing and hearing-impaired adults. The idealized classroom had simple geometry, uniform surface absorption, and an approximately diffuse sound field. It contained a speech source, a listener at a receiver position, and a noise source located at one of two positions. The relative output levels of the speech and noise sources were varied, along with the surface absorption and the corresponding reverberation time. The binaural impulse responses of the speech and noise sources in each classroom configuration were convolved with Modified Rhyme Test (MRT) and babble-noise signals. The resulting signals were presented to normal-hearing and hearing-impaired adult subjects to identify the configurations that gave the highest speech intelligibilities for the two groups. For both subject groups, when the speech source was closer to the listener than the noise source, the optimal reverberation time was zero. When the noise source was closer to the listener than the speech source, the optimal reverberation time included both zero and nonzero values. The results generally support previous theoretical results.     

Alkenes from terminal epoxides using lithium 2,2,6,6-tetramethylpiperidide and organolithiums or grignard reagents

E-Alkenes (including arylated alkenes, dienes, and allylsilanes) are efficiently prepared by alpha-deprotonation of terminal epoxides using lithium 2,2,6,6-tetramethylpiperidide, followed by in situ trapping with organolithiums or Grignard reagents.